This invention is generally directed to toner and developer compositions, and more specifically, the present invention is directed to developer and toner compositions comprised of an organometallic polymer, or a metallocene polymer wherein, for example, the metal is covalently bonded to the organic moiety, such as a ferrocenyl moiety present in the polymer backbone. In embodiments, there are provided in accordance with the present invention, toner compositions comprised, for example, of a metallocene polymer, carbon black, magnetites, or mixtures thereof, cyan, magenta, yellow, green, red or mixtures thereof, thereby providing for the development and generation of black and/or colored images. In embodiments, there are provided in accordance with the present invention thermoplastic polymers, such as styrene acrylates, styrene methacrylates, styrene butadienes, polyesters, polyamides, imide based resins, and other known toner resins, and wherein these polymers contain at least one metal containing moiety in an effective amount of from about 0.5 percent by weight to about 10 percent by weight of the polymer. The metals associated with an organic moiety are preferably a metal coordinated to an organic moiety, however, the metal may also be ionically or covalently bonded to the organic moiety, and wherein such metal includes, for example, iron, ruthenium, osmium, cobalt, rhodium, iridium, titanium and the like. The toners of the present invention in embodiments possess improved triboelectrification and excellent relative humidity stability characteristics. Also, the toner compositions of the present invention in embodiments can possess a number of other advantages such as exceptional nonvinyl resistance, low temperature fixing characteristics, such as from about 125.degree. C. to about 145.degree. C., and excellent temperature blocking characteristics, such as from about 55.degree. C. to about 65.degree. C.
In embodiments, the metal containing polymers of the present invention are comprised of resin containing therein, or more specifically in the resin backbone or as a pendant group, a coordinated metal, such as, for example, two cyclopentadienyl groups coordinated to a metal, such as iron (ferrocene) as illustrated by the formulas ##STR2## wherein M is iron (Fe), Co, Co+PF.sub.6-, Os, Ru, Ti, Rh, Zr, Hf, Sn, Cr, and the like. The aforementioned moieties are generally referred to as a metallocenes.
Moreover, the organometallic polymers of the present invention can, in embodiments, be comprised of a resin with chemically bonded metallocene groups wherein at least one of the metallocene groups is comprised of a moiety containing a coordinated metal, and wherein the moiety is, for example, an aryl ring like a substituted cyclopentadiene or substituted benzene ring as illustrated by the formulas ##STR3## wherein M is Co, Mo, W, Rh, Ti, Cu, Ir, Cr, Sn, Zr, Fe, Ru, Os, Nb and the like; L is a ligand such as CO, NO, alkyl with, for example, from 1 to about 25 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexy, octyl, decyl, trialkylphosphine, trialkylamine; and n is the number 1, 2, 3 or 4.
The resin composition of the present invention can in embodiments be generated by a process involving the melt condensation of about 1 mole equivalent of an organic diacid, an organic diester, or mixtures thereof, with at least 1 mole equivalent of an organic diol or mixtures of organic diols, provided that either or both diacid or diol component contain therein a metal containing monomer, such as dimethanol ferrocene, or ferrocene dicarboxylic acid and which is present in effective an amount of, for example, from about 0.01 to about 0.2 mole equivalent of the polymer resin. More specifically, the metal resin, such as a ferrocene-polyester, can be prepared, for example, by melt condensation by charging a reactor equipped with a mechanical stirrer and distillation apparatus with about 0.9 mole of a diester, such as dimethyl terephthalate, with about 0.1 mole of a metal containing moiety, such as 1,1'-ferrocene dicarboxylic acid, with about 2 moles of organic diol, such as 1,2-propanediol, and about 0.01 mole of catalyst, such as butylstannoic acid. The mixture is then heated to about 185.degree. C. for a duration of from about 3 to about 6 hours whereby a mixture of methanol and water is collected in the distillation receiver. The reaction temperature is then raised from 185.degree. C. to about 220.degree. C., and maintained at 220.degree. C. for a duration of from about 1 hour to about 6 hours under reduced pressure, whereby from about 0.8 mole to about 1 mole of the excess diol is collected in the distillation receiver. The product is then discharged from the reactor to yield, for example, the copoly(propylene-diethylene terephthalate)-copoly (1,3-dicarboxyl-ferrocene) resin.
Moreover, the resin composition of the present invention can in embodiments be generated by a process involving the anionic or free radical polymerization process of vinyl containing monomers such as styrene, isoprene, alkyl acrylates, alkyl methacrylates, butadiene mixtures thereof and a metal containing vinyl monomer, such as vinyl ferrocene, present in an effective amount of from about 0.1 to about 10 mole percent of the resin. The aforementioned metal containing polymers of the present invention in embodiments exhibit a number average molecular weight (M.sub.n) of from about 1,500 to about 100,000 and a weight average molecular weight (M.sub.w) of from about 3,000 to about 300,000 grams per mole as measured by gel permeation chromatography, and a glass transition temperature of from about 50.degree. C. to about 65.degree. C. as measured by the differential scanning calorimeter.
The toner compositions of the present invention in embodiments possess a number of advantages, including excellent relative humidity sensitivity, low melting characteristics, excellent blocking characteristics, excellent hot-offset temperatures, broad fusing latitudes, and nonvinyl offset properties.
A number of toner resins are known, such as styrene acrylates, styrene methacrylates, styrene butadiene, polyesters, polyamides, imide based resins, such as polyimides, polyester imides, polyimide imines, or polyamic acid, and the like. Metallocene or organometallic resins are illustrated in the Encyclopedia of Polymer Science and Engineering, 2nd Edition, Vol. 10, pages 541 to 594 (1985) published by John Wiley and Sons, the disclosure of which is totally incorporated herein by reference. Ferrocene containing polymers are disclosed in the aforementioned Encyclopedia of Polymer Science and Engineering, the disclosure of which is totally incorporated herein by reference. However, the use of organometallic containing polymers, especially ferrocene polymers, as a toner resin is not believed to be known.
In United Kingdom Patent Application GB 2 090 007, there is disclosed a light sensitive composition for a photorecording material, and wherein the photorecording material incorporates a ferrocene derivative and a halohydrocarbon. There is also disclosed in a Japanese Patent 5267042 an organic magnetic material for toners and ink comprised of a polymer derived from a ferrocene derivative and a benzene phosphonic acid ester. Other patent publications that may be of interest are Soviet Union 1029125, 1029124and 1029123, wherein there is disclosed the use of ferrocene polymers in photomechanical processes.